α—位取代的异色满—4—酮衍生物的合成

利用缩合反应合成出8种尚未见报道的α-位取代的异色满-4-酮衍生物,其结构均已经红外光谱、核磁共振谱及元素分析证实。     

卤盐离子液体/氧气催化芳硫酚与异色满反应

以1-羧乙基-3-甲基咪唑氯（[COOH-EtMIm][Cl]）/O2体系催化异色满与取代苯硫酚发生脱氢偶联反应,合成了1-(取代苯硫酚)异色满。通过单因素实验对反应影响因素进行筛选,得到最佳反应条件为：4-甲基苯硫酚（128 mg, 0.5 mmol）、异色满（134 mg, 1.0 mmol）、[COOH-EtMIm][Cl]（95 mg, 0.5 mmol）、氧气（0.1 MPa）、反应温度120 ℃、反应时间12 h。在该条件下,催化剂可重复使用4次,实现了1-(4-甲基苯硫酚)异色满克级合成,底物拓展后得到12种1-(取代苯硫酚)异色满,产率为52%~96%。并提出了[COOH-EtMIm][Cl]阴阳离子通过氢键分别活化苯硫酚与异色满,经O2氧化,脱氢得到1-(取代苯硫酚)异色满的反应机理。     

卤盐离子液体/氧气催化芳硫酚与异色满反应

以1-羧乙基-3-甲基咪唑氯（[COOH-EtMIm][Cl]）/O2体系催化异色满与取代苯硫酚发生脱氢偶联反应,合成了1-(取代苯硫酚)异色满。通过单因素实验对反应影响因素进行筛选,得到最佳反应条件为：4-甲基苯硫酚（128 mg, 0.5 mmol）、异色满（134 mg, 1.0 mmol）、[COOH-EtMIm][Cl]（95 mg, 0.5 mmol）、氧气（0.1 MPa）、反应温度120 ℃、反应时间12 h。在该条件下,催化剂可重复使用4次,实现了1-(4-甲基苯硫酚)异色满克级合成,底物拓展后得到12种1-(取代苯硫酚)异色满,产率为52%~96%。并提出了[COOH-EtMIm][Cl]阴阳离子通过氢键分别活化苯硫酚与异色满,经O2氧化,脱氢得到1-(取代苯硫酚)异色满的反应机理。     

异色满类化合物合成方法综述

1前言 异色满类化合物的合成方法有一步法、两步法和三步法。最具代表性的异色满类化合物为三环异色满麝香(Tricyclic isochromans),俗称佳乐麝香,化学名称为1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基-环戊基-γ-2-苯并吡喃(1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyrane)。由于其官能团是醚基,故它对光、碱的稳定性非常好,是良好的麝香香料。它具有异香豆酮类的三环结构,为无色透明的粘稠液体。沸点129℃(0.8mmHg),密度d_4~201.005,折光率nd201.5432。     

Friedlaender反应合成异喹啉并喹啉和异色满并喹啉

利用异喹啉酮和异色满酮与邻氨基苯甲醛的Ｆｒｉｅｄｌａｅｎｄｅｒ反应合成了４种新的异喹啉并喹啉和异色满并喹啉化合物。通过元素分析、红外光谱和核磁共振氢谱表征了新化合物的结构。     

三环异色满的合成

以α-甲基苯乙烯、叔戊醇为起始原料,经混酸催化缩合制取五甲基茚满,然后与环氧丙烷在三氯化铝催化下制得六甲基茚满醇,再经与多聚甲醛反应,环合成三环异色满,总收率39.5％;并对香气进行了纯化。     

异香豆素类衍生物的卤化烷氧基化反应

以N-溴代丁二酰亚胺(NBS)、N-氯代丁二酰亚胺(NCS)分别为溴代、氯代试剂,醇类化合物作为反应原料及溶剂,实现了异香豆素类衍生物3,4-位的卤化烷氧基化反应.室温(25℃)下即可在3,4-位之间发生加成反应,合成具有潜在药理活性的异色满-1-酮类衍生物.对4-溴-3-甲氧基-3-苯基异色满-1-酮(Ⅳa)的合成反...     

高效液相色谱法测定甲氧基丙烯酸酯类杀菌剂中间体3-异色酮的质量分数

针对目前国内暂无对甲氧基丙烯酸酯类杀菌剂活性基团的重要合成中间原料 3-异色酮检测方法的相关研究及报道,本试验建立了一种测定 3-异色酮质量分数的检测方法。采用高效液相色谱仪,以乙腈-超纯水为流动相,使用 ODS-SP 为填料的不锈钢色谱柱和二级阵列管检测器,在 210 nm 波长下对合成甲氧基丙烯酸酯类杀菌剂重要中间体 3-异色酮进行分离和定量分析。当 3-异色酮的质量浓度在 0.5～20 mg·L^-1时,分析方法的线性关系良好,相关系数 R²为 0.999,检出限为 3.55×10^-1 mg·L^-1,定量限为 1.18 mg·L^-1,土壤和水体中加标回收率均在 80%以上。该检测方法分离效果好,线性关系、精密度和回收率均符合要求,可作为 3-异色酮环境安全性评价时的质量分数测定方法,也可用于农药合成和生产环节的质量控制方法。     

罗匹尼罗中间体4-(2-苯甲酰氧乙基)-3-氯-1,3-二氢-2H-吲哚啉-2-酮的合成

以苯乙醇为原料,经分子内Friedel-Crafts烷基化反应合成了异色满,接着开环、成盐、水解得到苯甲酸-2-甲酰基苯乙基酯,再和硝基甲烷反应制备2-[2-（苯甲酰氧基）乙基]-β-硝基苯乙烯,最后通过Royer反应环合生成罗匹尼罗中间体4-（2-苯甲酰氧乙基）-3-氯-1,3-二氢-2H-吲哚啉-2-酮。产品经由薄层色谱、核磁共振谱、红外光谱分析,确为目的化合物,总收率为31．51％。     

制备异色满的方法

用β-苯乙醇和多聚甲醛为原料,进行了HC l催化法,三氯化铝催化法和对甲苯磺酸催化法的合成路线的实验,并对其反应机理进行了探讨,应用对甲苯磺酸催化法合成异色满的合成路线,得率46%,纯度96%。     

Insect antifeedant properties of anthranoids from the genusVismia

Vismiones and ferruginins, representatives of a new class of lypophilic anthranoids from the genusVismia were found to inhibit feeding in larvae of species ofSpodoptera, Heliothis, and inLocusta migratoria.     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Bark and Ambrosia Beetles in the Southeastern US

In 2002–2004, we examined the flight responses of 49 species of native and exotic bark and ambrosia beetles (Coleoptera: Scolytidae and Platypodidae) to traps baited with ethanol and/or (−)-α-pinene in the southeastern US. Eight field trials were conducted in mature pine stands in Alabama, Florida, Georgia, North Carolina, and South Carolina. Funnel traps baited with ethanol lures (release rate, about 0.6 g/day at 25–28°C) were attractive to ten species of ambrosia beetles (Ambrosiodmus tachygraphus, Anisandrus sayi, Dryoxylon onoharaensum, Monarthrum mali, Xyleborinus saxesenii, Xyleborus affinis, Xyleborus ferrugineus, Xylosandrus compactus, Xylosandrus crassiusculus, and Xylosandrus germanus) and two species of bark beetles (Cryptocarenus heveae and Hypothenemus sp.). Traps baited with (−)-α-pinene lures (release rate, 2–6 g/day at 25–28°C) were attractive to five bark beetle species (Dendroctonus terebrans, Hylastes porculus, Hylastes salebrosus, Hylastes tenuis, and Ips grandicollis) and one platypodid ambrosia beetle species (Myoplatypus flavicornis). Ethanol enhanced responses of some species (Xyleborus pubescens, H. porculus, H. salebrosus, H. tenuis, and Pityophthorus cariniceps) to traps baited with (−)-α-pinene in some locations. (−)-α-Pinene interrupted the response of some ambrosia beetle species to traps baited with ethanol, but only the response of D. onoharaensum was interrupted consistently at most locations. Of 23 species of ambrosia beetles captured in our field trials, nine were exotic and accounted for 70–97% of total catches of ambrosia beetles. Our results provide support for the continued use of separate traps baited with ethanol alone and ethanol with (−)-α-pinene to detect and monitor common bark and ambrosia beetles from the southeastern region of the US.     

Methyl 2,4,6-decatrienoates Attract Stink Bugs and Tachinid Parasitoids

Halyomorpha halys (Stål) (Pentatomidae), called the brown marmorated stink bug (BMSB), is a newly invasive species in the eastern USA that is rapidly spreading from the original point of establishment in Allentown, PA. In its native range, the BMSB is reportedly attracted to methyl (E,E,Z)-2,4,6-decatrienoate, the male-produced pheromone of another pentatomid common in eastern Asia, Plautia stali Scott. In North America, Thyanta spp. are the only pentatomids known to produce methyl 2,4,6-decatrienoate [the (E,Z,Z)-isomer] as part of their pheromones. Methyl 2,4,6-decatrienoates were field-tested in Maryland to monitor the spread of the BMSB and to explore the possibility that Thyanta spp. are an alternate host for parasitic tachinid flies that use stink bug pheromones as host-finding kairomones. Here we report the first captures of adult and nymph BMSBs in traps baited with methyl (E,E,Z)-2,4,6-decatrienoate in central Maryland and present data verifying that the tachinid, Euclytia flava (Townsend), exploits methyl (E,Z,Z)-2,4,6-decatrienoate as a kairomone. We also report the unexpected finding that various isomers of methyl 2,4,6-decatrienoate attract Acrosternum hilare (Say), although this bug apparently does not produce methyl decatrienoates. Other stink bugs and tachinids native to North America were also attracted to methyl 2,4,6-decatrienoates. These data indicate there are Heteroptera in North America in addition to Thyanta spp. that probably use methyl 2,4,6-decatrienoates as pheromones. The evidence that some pentatomids exploit the pheromones of other true bugs as kairomones to find food or to congregate as a passive defense against tachinid parasitism is discussed.     

2007～2008年世界塑料工业进展

收集了2007年7月～2008年6月世界塑料工业的相关资料,介绍了2007～2008年国外塑料工业的发展情况,提供了世界塑料产量、消费量及全球各类树脂的需求量及产能情况.按通用热塑性树脂(聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂)、工程塑料(尼龙、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚)、特种工程塑料(聚苯·硫醚、液晶聚合物、聚醚醚酮)、通用热固性树脂(酚醛、聚氨酯、不饱和聚酯树脂、环氧树脂)不同品种的顺序,对树脂的产量、消费量、供需状况及合成工艺、产品应用开发、树脂品种的延伸及应用的进一步扩展等技术作了详细介绍.     

2005～2006年国外塑料工业进展

收集了2005年7月～2006年6月国外塑料工业的相关资料,介绍了2005—2006年国外塑料工业的发展情况。提供了世界塑料产量、消费量及全球各类树脂生产量以及各国塑料制品的进出口情况。作为对比,介绍了中国塑料的生产情况。按通用热塑性树脂（聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂）、工程塑料（聚酰胺、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚）、通用热固性树脂（酚醛、聚氨酯、不饱和树脂、环氧树脂）、特种工程塑料（聚苯硫醚、液晶聚合物、聚醚醚酮）的品种顺序,对树脂的产量、消费量、供需状况及合成工艺、产品开发、树脂品种的延伸及应用的扩展作了详细的介绍。